JPH1060410A - Filler and filling using the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a filler excellent in adhesiveness, durability to injection pressure, having self extinguishing properties and no danger of ignitability, capable of forming a cured material of foam and to provide a filling method which does not stain hands and clothing and is preferable in terms of operation environment. SOLUTION: This filler is obtained by sealing separately a solution A containing an isocyanate and a solution B containing an alkali metal carbonate or an alkali metal silicate and water into a cylindrical container composed of two chambers. The filing method comprises removing a boundary of the two chambers of the cylindrical container in which the solutions A and B are separately sealed. The two chambers are made into one chamber to mix the solutions. The solution together with the cylindrical container is inserted into a gap, the container is destroyed to form a cured material of foam, which is filled into the gap. A liquid absorbing material is inserted into the front and the rear of the cylindrical container.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a filler and a filling method using the same, and more particularly to a filler comprising a urethane composition for filling gaps and a filling method using the same.

[0002]

2. Description of the Related Art Conventionally, a chemical solution using a cement-based chemical or a urethane-based chemical, which is conventionally used to inject a filler into cracked portions of a concrete building structure or the like and to solidify rocks in tunnel excavation work. In the injection method, the gap between the drilled hole and the injection bolt is filled to prevent leakage of the chemical solution, and when the leakage from various gaps is stopped, the gap is mainly filled with civil engineering or Performed in the architectural field. Various such filling methods are known, and each is used in consideration of economy, workability, and the like. As a filling method, a method of filling a cloth such as a waste, a method of filling a cement-based material, a method of filling a silicone-based filler, and a method of filling a cloth such as a waste with an organic material such as urethane are impregnated. Method and the like. However, the method of filling the cloth has a problem that it is difficult to completely fill the gap, and there is no adhesiveness to concrete, rock, soil and the like around the hole. In addition, in the method of filling the cement-based material, it takes a long time to cure, and the work of kneading with water is also required. There is a problem in that the properties are poor, and drying occurs after curing, and cracks occur after a long period of time. Further, in the method of infiltrating an organic material into a cloth such as a waste cloth and filling the cloth, it is necessary to perform a work of infiltrating the urethane chemical liquid into the waste cloth on site, and the workability is poor. The material has a problem that there is a danger such as a fire due to its flammability. In addition, the method of filling the silicone-based filler has a problem that the price of the filler is high and it is not economical to fill a relatively large gap.
In some cases, instead of filling, there is also a method of using a lid made of metal, plastic, wood, or the like.However, with the lid method, if the shape of the lid does not match the shape of the gap, the gap can be completely closed. However, there is a problem that it is difficult to block the irregular gap.

The inventor of the present invention has conducted various studies to solve the above-mentioned problems, and as a result, has found that the above-mentioned problems can be solved by filling a gap using a specific filler. Reached.

[0004]

That is, the present invention provides a solution A containing an isocyanate, an alkali metal carbonate or an alkali metal silicate and water, if necessary, a polyol, A reaction catalyst, and a liquid B containing one or more selected from the group consisting of foam stabilizers, and a filler separately sealed in a two-chamber cylindrical container; The boundaries between the two chambers of the cylindrical container in which the liquid A and the liquid B are separately sealed are taken, and the liquid A and the liquid B are mixed into one chamber and inserted into the gap together with the cylindrical container. Destroy the container,
This is a filling method for filling a gap by forming a foamed cured product, and a filling method for inserting a liquid-absorbing substrate before and / or after a cylindrical container.

Hereinafter, the present invention will be described in detail.

The filler according to the present invention forms a foamed cured product having high flame retardancy. The resulting foamed cured product is
It has excellent adhesion to concrete, rocks, soil, etc., has a self-extinguishing property of poor flammability, and has a low risk of fire due to ignition. And in the chemical solution injection method, when used to prevent leakage of the chemical solution,
Good durability against injection pressure. Further, since it has foaming properties, a large space can be filled with a small amount. Furthermore, the filler used in the present invention can appropriately change the size of the cylindrical container according to the size of the gap. During the construction, the liquid A and the liquid B are mixed inside the cylindrical container, and the mixture is separately poured into the gap. Or, it is easy to operate simply by stuffing it with a waste cloth, and is excellent in workability without fear of soiling of hands and clothes.

Although the isocyanates used in the present invention are not particularly limited, 4,4'-diphenylmethane diisocyanate (MDI), 2,4-tolylene diisocyanate (TDI), 1,3-xylylene diisocyanate (XDI), hexamethylene diisocyanate (HM
DI), polymethylene polyphenyl polyisocyanate (polymeric MDI), isocyanates such as 1,5-naphthalene diisocyanate (NDI), isocyanates obtained by modifying these isocyanates with water or lower monohydric or polyhydric alcohols, these isocyanates and various polyols Isocyanate consisting of a terminal isocyanate group-containing urethane prepolymer, a isocyanate obtained by modifying these terminal isocyanate group-containing urethane prepolymers with water or a lower monohydric or polyhydric alcohol, and these terminal isocyanate group-containing urethane prepolymers. Examples include isocyanates composed of one or a mixture of two or more of various isocyanates, and one or more of these can be used. Among them, use of polymeric MDI and urethane prepolymer having terminal isocyanate group is preferred in view of safety and economy.

The alkali metal carbonate (hereinafter referred to as alkali carbonate) used in the present invention includes potassium carbonate, sodium carbonate, lithium carbonate, sodium hydrogencarbonate, potassium hydrogencarbonate, and the like. The use of potassium carbonate is preferred from a good point of view. In addition, a suspension can be used if it is well mixed at the time of use. The amount of the alkali carbonate used is preferably 10 to 100 parts by weight, more preferably 25 to 75 parts by weight, based on 100 parts by weight of the isocyanate. If the amount is less than 10 parts by weight, sufficient strength and self-extinguishing properties may not be obtained. If the amount exceeds 100 parts by weight, the reaction may be too fast to adjust the curing time.

Examples of the alkali metal silicate (hereinafter referred to as alkali silicate) used in the present invention include water glass such as sodium silicate, potassium silicate, lithium silicate and the like. Use of water glass is preferred from the viewpoint of easy handling. In addition, a suspension can be used if it is well mixed at the time of use. Here, as the water glass, there are No. 1, No. 2 and No. 3 in the product standard, and a commercially available water glass can be used as it is. The use amount of the alkali silicate is preferably from 10 to 200 parts by weight, more preferably from 30 to 150 parts by weight, based on 100 parts by weight of the isocyanate. If the amount is less than 10 parts by weight, it is difficult to impart flame retardancy, and if it exceeds 200 parts by weight, the strength of the foamed cured product may decrease. When water glass is used, it is preferably 50 to 200 parts by weight, more preferably 80 to 150 parts by weight, based on 100 parts by weight of isocyanate. If it is less than 50 parts by weight, it is difficult to impart flame retardancy, and if it exceeds 200 parts by weight, the strength of the foamed cured product may be reduced.

The amount of water used is preferably 25 to 250 parts by weight, more preferably 30 to 100 parts by weight, based on 100 parts by weight of isocyanate. If it is less than 25 parts by weight, it will not be a suspension or solution, and the mixing of isocyanate will be poor, and the foamed cured product obtained may vary in expansion ratio and strength development.If it exceeds 250 parts by weight, it has flame retardancy. May decrease.

In the present invention, the foam hardening time can be adjusted,
In order to stabilize the foam uniformly, it is preferable to use one or more selected from the group consisting of polyols, reaction catalysts, and foam stabilizers on the liquid B side.

The polyols used in the present invention have a function as a surfactant for improving the reactivity between isocyanates and water, and specifically include polypropylene glycol, polyethylene glycol, and trimethylolethane. A polyol composed of an alkylene glycol such as trimethylolpropane, hexamethylene glycol, and castor oil; a polyol composed of an adduct obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to glycerin, sorbitol, and sucrose; ethylene oxide-propylene Polyol comprising an oxide copolymer, and ethylenediamine,
Examples of the polyol include adducts obtained by adding an alkylene oxide such as ethylene oxide or propylene oxide to amines such as diethanolamine, triethanolamine, and triethylenediamine, and one or more of these can be used. Among them, use of a polyol composed of an adduct of polypropylene glycol or ethylenediamine with propylene oxide added is preferred from the viewpoint of reactivity and strength. The amount of the polyol used is 5 parts per 100 parts by weight of the isocyanate.
It is preferably from 100 to 100 parts by weight, more preferably from 10 to 50 parts by weight. If the amount is less than 5 parts by weight, the foamed cured product may become brittle, and if it exceeds 100 parts by weight, the self-digestibility may decrease.

[0013] The reaction catalyst used in the present invention is a substance which promotes the action of obtaining a foamed cured product by the reaction of an isocyanate group, and can control the foaming curing time. Examples of the reaction catalyst include amine catalysts, organometallic catalysts, and inorganic catalysts.Each of these can be used, but inorganic catalysts and organometallic catalysts have a relatively low activity, and are therefore environmentally friendly. From the viewpoint of conservation, the use of an amine catalyst is preferred. Examples of the amine-based catalyst include ethylenediamine, triethylenediamine, triethylamine, ethanolamine, diethanolamine, and hexamethylenediamine or a derivative thereof, or a mixture with a solvent. Examples of the organometallic catalyst include dibutyltin dilaurate, dibutyltin diacetate, and potassium acetate, and examples of the inorganic catalyst include tin chloride. The amount of the reaction catalyst used is not particularly limited, but is preferably 0.1 to 100 parts by weight of isocyanates.
The amount is preferably 1 to 10 parts by weight, more preferably 0.5 to 5 parts by weight. If the amount is less than 0.1 part by weight, the reaction rate may be too slow to be practical, and if it exceeds 10 parts by weight, the reaction rate may be too high to impair the strength development of the foamed cured product.

The foam stabilizer used in the present invention refers to a foam stabilizer which is formed by reacting an alkali carbonate and / or an alkali silicate with an isocyanate to stabilize the foam uniformly, thereby increasing the expansion ratio. Is increased. When a foam stabilizer is not used, foam generated by the reaction may be destroyed, and the expansion ratio may be reduced. Examples of foam stabilizers include dimethylpolysiloxane, polyether-modified silicone such as dimethylpolysiloxane-polyoxypropylene copolymer, epoxy-modified silicone, amine-modified silicone, carboxyl-modified silicone, methacryl-modified silicone, and carbinol-modified silicone. Various modified silicone oils and the like can be mentioned, but dimethylpolysiloxane and / or
Alternatively, use of a polyether-modified silicone is preferred. The amount of the foam stabilizer is preferably 0.01 to 5 parts by weight, more preferably 0.05 to 3 parts by weight, based on 100 parts by weight of the isocyanates. If the amount is less than 0.01 part by weight, the expansion ratio may decrease. If the amount exceeds 5 parts by weight, the balance between foaming and curing may be lost.

In the present invention, further, in order to adjust the reaction characteristics and the characteristics of the foamed cured product, an anionic surfactant such as an alkylbenzene sulfonate, a cationic surfactant such as a quaternary ammonium salt, an organic acid or a salt thereof. Deodorizing substances such as salts, thickening substances such as methylcellulose,
It is also possible to use substances having a viscosity lowering effect, such as propylene carbonate and acetone.

In the present invention, the mixing ratio of the liquid A and the liquid B is
Solution B is preferably 50 to 300 parts by weight with respect to 100 parts by weight,
0 to 200 parts by weight is more preferred. If the amount is less than 50 parts by weight, the strength of the foamed cured product may not be obtained, and if it exceeds 300 parts by weight, the expansion ratio may be reduced.

In the present invention, the liquid A and the liquid B are used as a filler separately sealed in a cylindrical container divided into two chambers.

The material of the cylindrical container used in the present invention is not particularly limited, but a material that can be bent or rolled with a soft material such as plastic can be used. In addition, even if the material is a hard material such as a metal, it can be used as long as it can be bent or rolled by reducing its thickness, such as an aluminum foil. It is possible. The size of the cylindrical container is not particularly limited, and varies depending on the size of the hole of the gap to be inserted. For example, if the diameter of the hole is about 5 cm, it can be used without any problem if the length is about 20 to 80 cm and the width is about 1 to 10 cm. In particular, in the chemical solution injection method used for tunnel excavation work, usually, a hole with a diameter of 5 cm and a depth of 300 cm cut into the top end of the tunnel face has a diameter of 30 × length.
Insert a 300 cm injection bolt and inject the drug solution from the bolt. At this time, the clearance between the injection bolt and the hole must be closed so that the chemical solution does not leak from the hole.
In such a case, the dimensions of the cylindrical container are preferably 5 cm in width and 50 cm in length so that the injection bolt wound around the cylindrical container can be inserted.

The method for dividing the cylindrical container into two chambers is not particularly limited. For example, a boundary is formed with a stopper or the like, and the method is temporarily divided into two chambers or the cylindrical container is folded in half. If necessary, there is a method in which a stopper is attached so as not to mix the two liquids, one liquid is charged with the liquid A and the other liquid is charged with the other liquid, and both ends of the cylindrical container are sealed.

Here, the stopper is for separating the solution A and the solution B so that they do not mix. If the stopper can be completely separated before use and can be easily released when used. There is no particular limitation. As a stopper, a string-shaped stopper made of wire, chemical fiber, etc.
Clips, fasteners, tapes and the like,
It is preferable to use clips or tapes in terms of easy removal.

In the present invention, the liquid A and the liquid B are separately filled in a cylindrical container divided into two chambers and used as a filler. The total amount of the solution A and the solution B to be injected into the cylindrical container is not particularly limited, but varies depending on the volume of the hole to be filled. If the volume of the hole is 0.3 to 2 liters, the amount is about 100 to 500 g. I just want it.

The expansion ratio of the urethane composition of the filler of the present invention is preferably 3 times or more. If it is less than three times, the filling of the gap by foaming may not be sufficient. The curing time of the liquid mixture of the present invention varies depending on the temperature, but the foaming curing starts in about 30 to 120 seconds, and the pores can be closed in a short time. When the solution A and the solution B react, carbon dioxide gas is generated, and at the time of the reaction, since the reaction temperature becomes 50 to 100 ° C., water vapor is generated at the same time. The boundary of the cylindrical container of the filling inserted into the hole is destroyed from the inside by the generated gas. Further, if necessary, it can be broken by applying an external force such as a rod.

The method of filling the gap using the filler of the present invention is not particularly limited. For example, immediately before filling, the boundary separated into two chambers is removed to form one chamber, And liquid B, knead the cylindrical container with both hands for about 10 to 20 seconds, insert it into the filling point for each cylindrical container, make a few small holes with a reinforcing rod, etc., and drain the mixture. It should be easy. In addition, if the liquid absorbing base material is filled in advance, the mixed liquid does not leak to the depth of the gap, and if the filler is inserted and the liquid absorbing base material is filled, the mixed liquid may leak from the gap entrance. In addition, if the filler is arranged so as to be sandwiched between the liquid-absorbing base materials, it is possible to fill the space with almost no liquid leakage. The material itself is effective because it adheres to the rock or the like, or the mixed liquid is filled in the gaps between the liquid-absorbing base materials, thereby obtaining an adhesive effect and a sealing effect. Here, the liquid-absorbing base material is not particularly limited as long as the mixed solution can permeate and can be freely rounded or deformed, and examples thereof include rags and cotton.

In the present invention, the number of fillers to be inserted into the gap holes varies depending on the size of the holes, the injection pressure at the time of injecting the chemical solution, and the required durability, but usually one is sufficient and sufficient durability is provided. If necessary, two or three pieces may be used.

[0025]

The present invention will be described in more detail with reference to the following examples.

Example 1 Solution A was mixed with 100 parts by weight of isocyanate, and solution B was mixed with 50 parts by weight of alkali carbonate A and water in the amounts shown in Table 1 to prepare solution A and solution B. . The prepared liquid A and liquid B were mixed at a weight ratio of 1: 1 and the rise time, expansion ratio, and compressive strength of the obtained foamed cured product were measured. The results are also shown in Table 1.

<Materials> Isocyanates: Isocyanate-terminated urethane prepolymer obtained by reacting 200 parts by weight of polyethylene glycol having a molecular weight of 1,500 with 800 parts by weight of polymeric MDI Alkali carbonate A: potassium carbonate, commercially available

<Measurement method> Rise time: time from mixing of liquid A and liquid B to completion of foaming Expansion ratio: (total volume of liquid A and liquid B) / (maximum foaming of foamed cured product) Volume) Compressive strength: Filling a mixture of Liquid A and Liquid B in a mold frame of 2 cm in length, width and length, molding and leaving it at 20 ° C for 24 hours

[0029]

[Table 1]

Example 2 Except that 100 parts by weight of isocyanates were added to solution A, and 50 parts by weight of alkali carbonate A, water and α25 parts by weight of polyols shown in Table 2 were added to solution B. Example 1
The same was done. The results are also shown in Table 2.

<Materials used> Isocyanates: polymeric MDI, commercially available polyols α: triethanolamine with ethylene oxide added

[0032]

[Table 2]

Example 3 100 parts by weight of isocyanates on Liquid A side and Table 3 on Liquid B side
In the same manner as in Example 1, except that the following amounts of alkali silicate and polyols α25 parts by weight were blended. The results are also shown in Table 3.

<Materials> Alkali silicate: No. 3 water glass, commercially available

[0035]

[Table 3]

Example 4 Except that 100 parts by weight of isocyanates were added to the liquid A side, 50 parts by weight of alkali carbonate A and 50 parts by weight of water were added to the liquid B side, and the polyols α or β in the amounts shown in Table 4 were used. Example 1
The same was done. The results are also shown in Table 4.

<Materials> Polyols β: polypropylene glycol, commercially available

[0038]

[Table 4]

Example 5 Example 1 was repeated except that 100 parts by weight of an isocyanate was added to the side of the liquid A, 50 parts by weight of alkali carbonate A was added to the side of the liquid B, water having the amounts shown in Table 5 and 25 parts by weight of polyols were used. The same was done. The results are also shown in Table 5.

[0040]

[Table 5]

Example 6 100 parts by weight of isocyanates on the side of solution A, 50 parts by weight of alkali carbonate A, 50 parts by weight of water, and polyols α25 on the side of solution B
The procedure was performed in the same manner as in Example 1 except that the parts by weight and the reaction catalyst and the foam stabilizer shown in Table 6 were added. The results are also shown in Table 6.

<Materials used> Reaction catalyst: Tetramethylhexamethylenediamine, commercial product Foam stabilizer: Foam stabilizer for silicone-based highly elastic foam, commercial product

[0043]

[Table 6]

Example 7 Based on 100 parts by weight of solution A comprising isocyanates,
50 parts by weight of alkali carbonate A, 50 parts by weight of water, polyols α
The procedure was performed in the same manner as in Example 1 except that the amount of the liquid B consisting of 25 parts by weight, 0.5 parts by weight of the reaction catalyst, and 0.2 parts by weight of the foam stabilizer was used as shown in Table 6. The results are also shown in Table 7.

[0045]

[Table 7]

Example 8 Solution A comprising isocyanates and alkali carbonate A50
Parts by weight, 50 parts by weight of water, 25 parts by weight of polyols, 0.5 part by weight of a reaction catalyst, and 0.2 part by weight of a foam stabilizer were mixed with liquid B at a weight ratio of 1: 1. A filler made of aluminum foil having a length of 60 cm and a width of 4.5 cm, which was sealed as shown in Table 8, was prepared. Insert a 28 mm diameter injection bolt into a hole with a diameter of about 5 cm and a depth of 300 cm drilled to perform chemical injection, insert the created filler, and fill the gap at a depth of 30 cm from the entrance of the hole Tried. The filling method is to remove the tape used as a stopper, rub it for about 10 seconds with the cylindrical container, insert the filler to the depth of 30 cm from the hole while wrapping the filler around the injection bolt, and use a reinforcing rod to make a small hole in the cylindrical container. Two places were opened, foamed and hardened, the filling state was observed, and the rise time was measured. Table 8 shows the results. In addition, the time required for filling the holes was 1-2 minutes without soiling the hands and clothes during the filling. As described above, it was recognized that the method using the filler of the present invention was simple and had good workability.

<Measurement method> Filling condition: The case where the outflow of the mixed liquid to the entrance of the hole was small and the hole was completely sealed was regarded as good.

[0048]

[Table 8]

Example 9 Filling was carried out in the same manner as in Example 8 except that the filler was used in which the total amount of the liquid A and the liquid B was 200 g, and the stopper was removed after the waste was packed into the opening of the hole. did. After two small holes were made in the cylindrical container with a bar of reinforcing steel, a waste was further filled and foam-hardened, and then a cement-based chemical was injected from an injection bolt. As a result, the injection pressure of the cement-based chemical was about 10 kg / cm ² , but no leakage of the cement-based chemical from the filling point was observed, and the time required to fill the holes was as short as 1-2 minutes. There were no stains on my hands or clothes. For comparison, when the gap was filled only with the waste without using the filler, the cement-based chemical liquid leaked immediately after the start of the injection. Also, without using the filler of the present invention, a gap filling method was carried out in which a liquid A and a liquid B were mixed on site with a bucket, soaked into a waste, and the waste was filled into a gap. In this method, the time required for soiling the hands and clothes and filling the holes was 3 to 4 minutes.

[0050]

By using the filler of the present invention,
It is possible to reliably fill the gap. In addition, the foamed cured body formed in the gap has excellent adhesiveness to concrete, rock, soil, and the like, and thus has good durability against injection pressure during chemical injection. Further, since the obtained foamed cured product is self-extinguishing, there is no danger of ignition.
And since a foaming hardening body is formed in several minutes, even if water exists, construction is possible. Furthermore, since it can be mixed and inserted into the filling location for each cylindrical container, hands and clothes are not stained, which is preferable in the working environment and the construction speed is high. Since the foamed cured product is formed, it is not necessary to fill the urethane composition in an amount corresponding to the volume of the gap, and it is possible to fill the urethane composition in a smaller amount, which is economically advantageous.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Agency reference number FI Technical display location // (C08G 18/08 101: 00) (72) Inventor Sakae Kawasaki 306 Koyagicho, Takasaki City, Gunma Prefecture Address: Inside C.R.K. Co., Ltd. (72) Inventor Kiyonobu Maruhashi 306, Koyagi-cho, Takasaki-shi, Gunma C.R.K.

Claims (4)

[Claims] 1. A solution containing an isocyanate and a solution B containing an alkali metal carbonate or an alkali metal silicate and water are separately sealed in a two-chamber cylindrical container. A filling material characterized by comprising: 2. The packing according to claim 1, further comprising one or more selected from the group consisting of a polyol, a reaction catalyst, and a foam stabilizer in the liquid B. 3. A boundary between two chambers of a cylindrical container in which the liquid A and the liquid B according to claim 1 or 2 are separately sealed, and the liquid A and the liquid B are mixed in one chamber. Filling the gap by inserting the cylindrical container into the gap, breaking the cylindrical container, and forming a foamed cured product. 4. The filling method according to claim 3, wherein the liquid-absorbing substrate is inserted before and / or after the cylindrical container.